CN102783255A - Copper foil for printed circuit board and copper-clad laminate for printed circuit board - Google Patents

Copper foil for printed circuit board and copper-clad laminate for printed circuit board Download PDF

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Publication number
CN102783255A
CN102783255A CN2011800107713A CN201180010771A CN102783255A CN 102783255 A CN102783255 A CN 102783255A CN 2011800107713 A CN2011800107713 A CN 2011800107713A CN 201180010771 A CN201180010771 A CN 201180010771A CN 102783255 A CN102783255 A CN 102783255A
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China
Prior art keywords
copper
copper foil
zinc
quality
adhesion amount
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CN2011800107713A
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CN102783255B (en
Inventor
森山晃正
石井雅史
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Abstract

Disclosed is a copper foil for printed circuit boards which comprises a copper foil and, deposited on a surface thereof, a layer comprising nickel, zinc, and copper (hereinafter, referred to as "copper-nickel-zinc layer"), characterized in that the amount of deposited zinc in the copper-nickel-zinc layer is 200-2,000 [mu]g/dm2 and that in the copper-nickel-zinc layer, the amount of Ni is 1-50 wt.%, (amount of deposited zinc (mass%))/{100-(amount of deposited copper (mass%))} is 0.3 or more, and (amount of deposited copper (mass%))/{100-(amount of deposited zinc (mass%))} is 0.3 or more. A method for treating a surface of a copper foil has been established with which it is possible to effectively prevent a circuit erosion phenomenon that occurs when a copper foil laminated to a resin base is subjected to soft etching of a circuit with a sulfuric acid/hydrogen peroxide etchant.

Description

Tellite is used copper clad laminate with Copper Foil and tellite
Technical field
The present invention relates to a kind ofly have good heat resistance and chemical sproof tellite is used copper clad laminate with Copper Foil and tellite, relate in particular to a kind of Copper Foil have the layer that contains nickel, zinc and copper (below be called " copper nickel zinc layer ") at least with on the adhesive surface of resin, have on layer chromate by rete, and the tellite that has silane coupling agent layer as required with Copper Foil, and the tellite of this Copper Foil manufacturing of use use copper clad laminate.
Background technology
As a kind of conductor package substrate of tellite, be the tellite that is used to install semiconducter IC chip, other semiconductor elements.It is tiny that the circuit that on conductor package substrate, forms is compared with common tellite, therefore uses the resin base material different with common tellite as baseplate material.
Conductor package substrate is usually through following technology manufacturing.At first, Copper Foil is adhered in the HTHP laminated on the base materials such as synthetic resin.Be referred to as copper clad laminate, or abbreviate laminated sheet as.Then, in order on laminated sheet, to form electroconductive circuit as purpose, through materials such as elching resistant resins, printing and the equal pattern of circuit on Copper Foil.Then, remove the unwanted part of the Copper Foil that exposes through etch processes.
Remove Printing Department after the etching, on substrate, form the circuit of conductivity.On the circuit of formed conductivity, the element of final welding regulation and form the various tellites that electronic equipment is used.Finally, engage with etchant resist or lamination (build up) resin substrate.
Generally speaking, to tellite with the quality requirement of Copper Foil the adhesive surface bonding (so-called matsurface) with resin base material, and non-adhesive surface (so-called glassy surface) in different, need satisfy both simultaneously.
Requirement to glassy surface is: can oxidation stain when (1) outward appearance well reaches and preserves; (2) solder wettability (solder wettability) is good; (3) can oxidation stain during heat; (4) good etc. with the adherence of etchant resist.
On the other hand, the requirement to matsurface mainly comprises: can oxidation stain when preserve (1); (2) after heat, wet treatment, soldering, medicine processing etc., also abundant with the peel strength of base material; (3) can not occur with base material lamination, etching after the so-called lamination stain that produces etc.
And,, require the low roughening of copper foil surface in recent years along with the granular of circuit printed patterns.
Moreover in the electronic equipment of personal computer, mobile communicating etc., along with high speed, the high capacity of communication, electronic signal is high frequencyization day by day, and requirement can corresponding with it tellite and Copper Foil.When the frequency of electronic signal is 1GHz when above, electric current only flows through influence conductive surface, skin effect and becomes obviously, can't ignore the influence that impedance increases that changes of concavo-convex electric current transfer path because of the surface.From this point, also require the surface roughness of Copper Foil less.
In order to tackle above-mentioned requirements, tellite with Copper Foil the kinds of surface processing method has been proposed.
Surface treatment method is different in rolled copper foil and electrolytic copper foil, and the example as the surface treatment method of electrolytic copper foil comprises following method.
That is, at first,, generally will append to (roughened) after the copper foil surface, form refractory layers (obstacle parietal layer) such as brass or zinc in order to make it have thermal endurance by the particulate that copper and cupric oxide constitute for the bonding force (peel strength) that improves copper and resin base material.
Then, last, for prevent to transport or the keeping process in surface oxidation etc., handle antirust processing such as perhaps electrolytic zinc chromate processing through implementing dipping or electrolysis chromate down, form product.
Wherein, especially forming the surface treatment method of refractory layer, is vital as the method that determines copper foil surface character and state.Therefore, as the metal or alloy that forms refractory layer, a plurality of Copper Foils that formed coatings such as Zn, Cu-Ni alloy, Cu-Co alloy and Cu-Zn alloy are by practicability (for example, with reference to patent documentation 1).
Wherein, the Copper Foil that has formed the refractory layer that is made up of Cu-Zn alloy (brass) is widely used in the industry because of having following superperformance: when being used in the tellite that is made up of epoxy resin etc., do not have the spot of resin bed; The deterioration of the peel strength of the Copper Foil of tellite after at high temperature keeping is less etc.To forming the method for this refractory layer that constitutes by brass, in patent documentation 2, detail.
But; In recent years; In the manufacturing process of tellite, especially base plate for packaging; In order to improve etchant resist or laminated resin substrate and as the adherence of the glassy surface of the Copper Foil of circuit face; Bring into use mixed liquor through sulfuric acid and hydrogen peroxide to carry out soft etching and the Copper Foil glassy surface carried out the processing of roughening; If with the use of putting down in writing in patent documentation 1 grade be formed with the Copper Foil of known refractory layer the mixed liquor of copper foil circuit glassy surface through above-mentioned sulfuric acid and hydrogen peroxide of tellite carry out soft etching, erosion (circuit erosions) phenomenon of the previous circuit pattern both side ends (edge portion) that forms then takes place, therefore the problem of the peel strength deterioration of existence and resin base material.
This circuit erosion is meant that the adhesion side interlayer of copper foil circuit and resin base material is corroded by the mixed liquor of above-mentioned sulfuric acid and hydrogen peroxide, thus the phenomenon of the obvious deterioration of peel strength of the Copper Foil of this part.And if this phenomenon takes place on the entire circuit pattern, then circuit pattern is peeled off and is become serious problem from base material.
Therefore, as the surface-treated layer that can prevent the circuit erosion well, know that usually nickel-zinc-copper the layer that has added nickel in the brass is comparatively effective.But; Though the interpolation through nickel can prevent the circuit erosion; But the inventor finds: according to the difference of the addition of nickel, exist thermal endurance (heat-resisting peel strength) to descend or superficial layer that the residual generation of circuit when forming etc., reason Cu-Zn alloy (brass) constitute and produce the situation of deterioration.
The prior art document
Patent documentation
Patent documentation 1: the special public clear 51-35711 communique of Japan
Patent documentation 2: the special public clear 54-6701 communique of Japan
Summary of the invention
The problem that invention will solve
Problem of the present invention is a kind of Copper Foil of exploitation; This Copper Foil do not make the superficial layer that constitutes by Cu-Zn alloy (brass) each characteristic (the normality peel strength of the Copper Foil of lamination Copper Foil and resin base material and the tellite made, and with printed circuit board (PCB) at high temperature keep after the stipulated time peel strength (below be called heat-resisting peel strength), and drug resistance (hydrochloric acid)) deterioration and alleviate the foregoing circuit erosion, be suitable as the conductor package substrate use.
Especially; Establish the process for treating surface of the Copper Foil below a kind of; Promptly; When using sulfuric acid-hydroperoxide kind etching solution to come soft etched circuit when significantly improving heat-resisting peel strength, can prevent the circuit erosion (following be also referred to as as required " drug resistance ") of this etching solution effectively at resin base material laminated Copper Foil.
The means that are used to deal with problems
In order to address the above problem; The inventor has carried out wholwe-hearted research to carrying out surface-treated condition etc. on the Copper Foil, and the result finds: following Copper Foil to heat-resisting peel strength raising and drug resistance, be that the erosion resisting (anti-circuit aggressivity) of the matsurface of sulfuric acid-hydroperoxide kind etching solution during to the thin-skinned etching of Copper Foil gloss is comparatively effective.
Therefore, the present invention provides:
1) a kind of tellite is used Copper Foil, has the layer (below be called " copper nickel zinc layer ") that contains nickel, zinc and copper on the surface of Copper Foil, it is characterized in that the zinc adhesion weight of the per unit area of above-mentioned copper nickel zinc layer is 200 μ g/dm 2More than and 2000 μ g/dm 2Below, in the above-mentioned copper nickel zinc layer, Ni is 1 ~ 50 weight %, and (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is more than 0.3, and (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is more than 0.3.
And the present invention provides:
2) use Copper Foil according to above-mentioned 1 described tellite, it is characterized in that, on above-mentioned copper nickel zinc layer, have chromate by rete.
3) use Copper Foil according to above-mentioned 3 described tellites, it is characterized in that, above-mentioned chromate by rete in, the chromium adhesion weight of per unit area is 30 μ g/dm 2More than and 100 μ g/dm 2Below.
4) use Copper Foil according to above-mentioned 2 or 3 described tellites, it is characterized in that, also have silane coupling agent layer on by rete at above-mentioned chromate.
5) use Copper Foil according to each described tellite in above-mentioned 1 ~ 5, it is characterized in that Copper Foil is an electrolytic copper foil, on the matsurface when above-mentioned copper nickel zinc layer is formed on the electrolysis plating or the glassy surface of electrolytic copper foil.
6) use Copper Foil according to each described tellite in above-mentioned 1 ~ 5, it is characterized in that Copper Foil is a rolled copper foil.
7) a kind of tellite is used copper clad laminate, and each described tellite is processed with resin with Copper Foil and tellite in bonding above-mentioned 1 ~ above-mentioned 7.
The invention effect
As implied above, tellite of the present invention uses copper nickel zinc layer with Copper Foil for the peel strength deterioration that does not make the Copper Foil after tellite high temperature kept.So, can improve the heat-resisting peel strength of Copper Foil tremendously.
In addition; So can effectively prevent the circuit erosion of medicine; Especially be endowed and can have improved this new characteristic of anti-sulfuric acid-hydrogen peroxide property, as tellite with Copper Foil (especially conductor package substrate is used Copper Foil), and bonding Copper Foil and resin base material and the copper clad laminate (especially conductor package substrate is used copper clad laminate) that produces is very effective.Certainly, also can be used as common tellite uses with Copper Foil.
Description of drawings
Fig. 1 is the figure that is suitable for component zone of the present invention of expression Cu-Ni-Zn ternary alloy three-partalloy.
Embodiment
Below for easy to understand the present invention, the present invention specifically and at length is described.
Copper Foil of the present invention can use any one of electrolytic copper foil and rolled copper foil, under the situation of electrolytic copper foil, and the matsurface in the time of can being applicable to the electrolysis plating or the glassy surface of electrolytic copper foil.And, can also further implement roughened to their surface.For example, be purpose with (Peel) intensity of peeling off that improves the Copper Foil behind resin base material and the lamination, can directly use the electrolytic copper foil of roughened that the copper foil surface after the degreasing is for example applied the electro-deposition of " joint pimple " shape that carries out copper.
Generally speaking, in the manufacturing installation of the electrolytic copper foil of drum type, one-sided (drum side) is glassy surface, and an opposite side is a matsurface.In rolled copper foil, all are glossiness rolling surfaces.In the present invention, electrolytic copper foil comprises matsurface and glassy surface, can directly use during matsurface.To the glassy surface of electrolytic copper foil,, can implement roughened and form matsurface in order further to improve peel strength.
In rolled copper foil, implement roughened too.Roughened all can used known roughened under the situation arbitrarily, does not have especially to limit.
Matsurface of the present invention is meant the electrolytic copper foil of the matsurface with electrolysis when plating or implemented the electrolytic copper foil and the rolled copper foil of roughened, applicable to Copper Foil arbitrarily.
As stated, conductor package substrate of the present invention with Copper Foil by be formed on become with the copper nickel zinc layer of the copper foil surface of the adhesive surface of resin, chromate by rete (chromate film), and in case of necessity silane coupling agent layer constitute.As Copper Foil, can use the rolling Copper Foil or electrolytic copper foil.
In addition, chromate by rete can use electrolytic chromate by rete or the dipping chromate by rete.
As stated, the present invention for example forms the layer that contains nickel, zinc and copper (below be called " copper nickel zinc layer ") on the surface of Copper Foil.
In order to make the peel strength deterioration not after the Copper Foil heat, the zinc adhesion amount of the per unit area of the Copper Foil in the above-mentioned copper nickel zinc layer need be 200 μ g/dm 2More than.This be because, regardless of the component of copper nickel zinc layer, when the zinc adhesion weight less than 200 μ g/dm 2The time, the effect that layer forms disappears, and it is big that the deterioration of the peel strength after the heat becomes.On the other hand, surpass 2000 μ g/dm when the zinc adhesion amount 2The time, sulfuric acid-hydroperoxide kind etching solution becomes obvious to the erosion of circuit end.Therefore, the preferred 200 μ g/dm of zinc adhesion amount of the per unit area of the Copper Foil in the above-mentioned copper nickel zinc layer 2More than and 2000 μ g/dm 2Below.
Moreover; The inventor finds: in copper nickel zinc layer; The balance of the component of each metal is very important, the copper nickel zinc layer of the regional X shown in the component zone of the Cu-Ni-Zn ternary alloy three-partalloy through forming Fig. 1, and the peel strength after the heat, drug resistance (salt tolerant is acid, anti-sulfuric acid-hydrogen peroxide property) are good.Below specifically discuss.
In order to realize drug resistance, adding nickel is that inevitably the nickel ratio in the copper nickel zinc layer is to get final product more than 1%.When less than 1% the time, can't effectively prevent the circuit erosion.And when the nickel ratio in the copper nickel zinc layer surpassed 50%, the zinc in the following copper nickel zinc layer, the balance of copper were broken, and heat-resisting peel strength descends, and the residual pilosity when circuit forms is therefore not preferred.Therefore the nickel ratio in the copper nickel zinc layer is preferred more than 1% and below 50%.
Moreover the nickel ratio in the copper nickel zinc layer is more than 1% and 50% when following, the ratio of the zinc in the copper nickel zinc layer and the adhesion amount of copper exerts an influence to heat-resisting peel strength, drug resistance (hydrochloric acid).Particularly, need to satisfy following formula.That is, (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } (formula 1) is more than 0.3, and (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } (formula 2) is (the X zone of Fig. 1) more than 0.3.In addition, for easy to understand, following formula is added (formula 1) and (formula 2) respectively.
For example; When the zinc adhesion amount is too much; (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } (formula 1) is more than 0.3, but the copper adhesion amount tails off, and there is the situation (the regional c of Fig. 1) less than 0.3 in therefore (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } (formula 2).In this case, with respect to the zinc adhesion amount, the copper adhesion amount tails off, so drug resistance (hydrochloric acid) descends.
On the other hand; When the copper adhesion amount is too much; (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } (formula 2) is more than 0.3, but there is the situation (the regional b of Fig. 1) less than 0.3 in (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } (formula 1).
In this case, relative copper adhesion amount, the zinc adhesion amount tails off, and therefore heat-resisting peel strength descends.Therefore; The ratio of the zinc in the copper nickel zinc layer and the adhesion amount of copper preferably satisfies following two formula: (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } (formula 1) is more than 0.3, and (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } (formula 2) is (the X zone of Fig. 1) more than 0.3.
Copper nickel zinc layer forms with following condition usually.But, be 200 μ g/dm so long as can realize the zinc adhesion weight of the per unit area of copper nickel zinc layer 2More than and 2000 μ g/dm 2Below; In the above-mentioned copper nickel zinc layer; Ni is 1 ~ 50 weight %, and (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } (formula 1) is more than 0.3, and (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } (formula 2) is the plating condition more than 0.3; Then not special the qualification also can be used other plating conditions.
(bath composition)
With Ni:0.1g/L ~ 30g/L, Zn:0.1g/L ~ 12g/L, Cu:0.1g/L ~ 2g/L, sulfuric acid (H 2SO 4): 0.1g/L ~ 10g/L is basic plating bath.And, also alternative sulfuric acid and use other inorganic acids or organic carboxyl acid (citric acid, malic acid etc.)
(current density) 3 ~ 25A/dm 2
Next is that chromate is handled, this chromate by the making of rete in, also applicable electrolytic chromate is handled, the dipping chromate is handled, and the chromic acid salt bath in contain zinc zinc chromate any one in handling.
In either event, at the chromium adhesion amount less than 30 μ g/dm 2Down, it is less to increase acid resistance and stable on heating effect, therefore the chromium adhesion weight is made as 30 μ g/dm 2More than.And, when the chromium adhesion weight surpasses 100 μ g/dm 2The time, the effect that chromate is handled is saturated and the chromium adhesion weight can further not increase.In sum, the chromium adhesion weight of per unit area is preferably 30 ~ 100 μ g/dm in the chromate processing layer 2
Below record is used to form above-mentioned chromate by the example of the condition of rete.But as stated, be not limited to this condition, can use any one known chromate to handle.
Generally speaking, when the dipping chromate is handled, can realize chromium adhesion amount 30 ~ 40 μ g/dm of per unit area 2And when electrolytic chromate is handled, can realize chromium adhesion amount 30 ~ 100 μ g/dm of per unit area 2
This antirust processing is one of factor of impacting of acid resistance and the thermal endurance to Copper Foil, handles drug resistance and the thermal endurance that improves Copper Foil through chromate, and is therefore comparatively effective.
(a) example of dipping chromate processing
CrO 3Perhaps K 2Cr 2O 7: 1 ~ 12g/L, Zn (OH) 2Perhaps ZnSO 47H 2O:0 ~ 10g/L, Na 2SO 4: 0 ~ 20g/L, pH2.5 ~ 12.5, temperature: 20 ~ 60 ℃, time: 0.5 ~ 20 second
(b) example of electrolytic chromate processing
CrO 3Perhaps K 2Cr 2O 7: 1 ~ 12g/L, Zn (OH) 2Perhaps ZnSO 47H 2O:0 ~ 10g/L, Na 2SO 4: 0 ~ 20g/L, pH2.5 ~ 12.5, temperature: 20 ~ 60 ℃, current density: 0.5 ~ 5A/dm 2, the time: 0.5 ~ 20 second
, for example preferably contain tetraalkoxysilane more than a kind at least and possess the alkoxy silane that has with reactive functional group of resin with the silane coupler that uses in the Copper Foil as tellite of the present invention.The selection of this silane coupler is arbitrarily, and preferred consideration is selected with the adhesiveness of resin.
Moreover the present invention provides above-mentioned 1) ~ 7) any described tellite with Copper Foil and 8) described bonding tellite is with Copper Foil and resin base material and the copper clad laminate of making.
Then, handle (after the coating, carrying out drying) to implementing silane coupler on this antirust coat.
The condition that silane coupler is handled is following.The aqueous solution that will contain 0.5 volume % epoxy radicals silicone hydride is adjusted to pH7 and is coated with, and carries out drying afterwards.
(test method)
Use following 2 kinds with the resin base material of Copper Foil lamination:
FR-4 resin (glass fabric base material epoxy resin)
BT resin (triazine-bismaleimide amine resins, trade (brand) name: the GHPL-830 that Mitsubishi's aerochemistry is made)
In addition, BT resin thermal endurance is strong, is the material that in semiconductor package type printed circuit substrate, uses.
(1) the normality peel strength of FR-4 substrate and the mensuration of heat-resisting peel strength have been used
To the formation of lamination Copper Foil copper nickel zinc layer face and FR-4 resin base material and Copper Foil on the laminated sheet made carries out etching, on laminated sheet, form the wide copper foil circuit of 10mm.
Peel off this circuit, measure the normality peel strength.Then, the laminated sheet of having measured with above-mentioned formation the wide copper foil circuit of 10mm in atmosphere 180 ℃ after heating 2 days down peel strength (below be called heat-resisting peel strength) and with respect to the relative deterioration rate (loss %) of its normality peel strength.The FR-4 substrate is compared poor heat resistance with the BT substrate.
Therefore, have good heat-resisting peel strength and lower deterioration rate during as if use FR-4 substrate, also have sufficient heat-resisting peel strength and deterioration rate when then using the BT substrate.
(2) use the normality peel strength of BT substrate and the mensuration of the hydrogen peroxide of anti-sulfuric acid property
Lamination has been formed Copper Foil copper nickel zinc layer face and BT resin substrate and Copper Foil on the laminated sheet made carries out etching, on laminated sheet, form the wide copper foil circuit of 0.4mm.Peel off this circuit and measure the normality peel strength.Then, use the laminated sheet that has formed the wide copper foil circuit of above-mentioned 0.4mm, carry out anti-sulfuric acid-hydrogen peroxide property test and salt tolerant acid test.
In anti-sulfuric acid-hydrogen peroxide property test; With the copper foil circuit on the laminated sheet be impregnated into contain sulfuric acid 5 ~ 20 volume %, and the etching solution of hydrogen peroxide 1 ~ 10 volume % in; Behind copper foil circuit thickness etching 2 μ m, measure peel strength and its relative deterioration rate (loss %) with respect to the normality peel strength.
The mensuration of peel strength of this moment is under harsh environment, to carry out, and is that harsh condition is compared in the drug resistance assessment of carrying out usually when using the FR-4 substrate.Therefore, if when using the BT substrate, have good anti-sulfuric acid-hydrogen peroxide property, then in the FR-4 substrate, also has sufficient drug resistance (especially anti-sulfuric acid-hydrogen peroxide property).
In salt tolerant acid test, the copper foil circuit on the laminated sheet flood 90 minutes in containing 60 ℃ the solution of hydrochloric acid 12 weight % after, measure its peel strength and its relative deterioration rate (loss %) with respect to the normality peel strength.
(3) mensuration of the plating adhesion weight of the nickel of per unit area and zinc
Be exposed to mode and the FR-4 resin base material lamination on surface and produce laminated sheet with the face that has formed copper nickel zinc layer on the Copper Foil.Then, the copper of the copper nickel zinc layer through will being exposed to laminate surface and its female layer carries out the chemical analysis of the zinc concentration in the lysate with hydrochloric acid or nitric acid dissolve, measures the adhesion weight of the zinc of per unit area.
(4) parsing that has ratio of zinc, nickel and copper
Nickel, zinc and the copper that uses XPS (X linear light electronics optical spectroscopy) to measure to contain in the copper nickel zinc layer have a ratio.Mensuration is to carry out in the following manner; Promptly; In the time of through argon ion sputtering etching copper thickness; Carry out intermittently till copper layer from surface as the substrate of copper nickel zinc layer, to the nickel, zinc and the copper that obtain in each degree of depth exist ratio with carrying out integration apart from the degree of depth on surface, in copper nickel zinc layer integral body, on average have ratio thereby calculate nickel, zinc and copper.
The equipment that uses in the mensuration is the AXIS-HS of KRATOS manufactured, and argon ion sputtering is output as 52.5W.Under this condition, 1 minute about etching
Figure BDA00002048136200121
sputtering time of copper thickness is 15 ~ 100 minutes a condition.
Embodiment
Then, illustrative embodiment and comparative example.Its result is presented in following each table.In addition, present embodiment is represented a preferred example, and the present invention does not receive the qualification of this embodiment.Therefore, the distortion that comprises in the technological thought of the present invention, other embodiment or execution mode are all within the scope of the present invention.
In addition, in order to compare, put down in writing comparative example with the present invention.
(embodiment 1 ~ 9)
The electrolytic copper foil of used thickness 12 μ m is in the matsurface (surface average roughness: 3.8 μ m), form copper nickel zinc layer with following condition through electroplating of this Copper Foil.Nickel, zinc, copper exist ratio as shown in table 1.
(the electroplate liquid component of embodiment 1)
Ni:3g/L, Zn:6g/L, Cu:0.5g/L, sulfuric acid (H 2SO 4): 7.5g/L
(the electroplate liquid component of embodiment 2)
Ni:20g/L, Zn:3g/L, Cu:0.2g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of embodiment 3)
Ni:13g/L, Zn:1g/L, Cu:2g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of embodiment 4)
Ni:10g/L, Zn:12g/L, Cu:0.2g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of embodiment 5)
Ni:28g/L, Zn:8g/L, Cu:0.5g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of embodiment 6)
Ni:10g/L, Zn:5g/L, Cu:1.0g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of embodiment 7)
Ni:0.3g/L, Zn:0.3g/L, Cu:2.0g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of embodiment 8)
Ni:28g/L, Zn:1g/L, Cu:0.8g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of embodiment 9)
Ni:7g/L, Zn:10g/L, Cu:0.5g/L, sulfuric acid (H 2SO 4): 8.5g/L
(current density) 5A/dm 2Perhaps 10A/dm 2
Moreover, on this copper nickel zinc layer, carry out chromate and handle and the formation antirust coat.Below represent treatment conditions.
CrO 3: 4.0g/L, ZnSO 47H 2O:2.0g/L, Na 2SO 4: 15g/L, pH:4.2, temperature: 45 ℃, current density: 3.0A/dm 2, the time: 1.5 seconds
(embodiment 1)
In embodiment 1, the zinc in the plated film (Zn) adhesion amount is 924 μ g/dm 2, in the plated film, Ni:9 weight %; Zn:42 quality %, Cu:49 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.83; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.85, all in condition and range of the present invention.Consequently, in this embodiment 1, the peel strength in the normality BT substrate in the FR substrate is 1.47kN/m, and the peel strength after aging was 1.20kN/m in 2 days, and the deterioration rate is 18%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 1.05kN/m, and the peel strength after the salt acid treatment is 0.85kN/m; The deterioration rate is 20%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.98kN/m; The deterioration rate is 7%, all is good results.
Above result is as shown in table 1.
(table 1)
(embodiment 2)
In embodiment 2, the zinc in the plated film (Zn) adhesion amount is 320 μ g/dm 2, in the plated film, Ni:31 weight %; Zn:34 quality %, Cu:36 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.52; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.54, all in condition and range of the present invention.Consequently, in this embodiment 2, the peel strength in the normality BT substrate in the FR substrate is 1.56kN/m, and the peel strength after aging was 1.42kN/m in 2 days, and the deterioration rate is 9%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 0.99kN/m, and the peel strength after the salt acid treatment is 0.89kN/m; The deterioration rate is 10%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.86kN/m; The deterioration rate is 14%, all is good results.
Above result is shown in table 1 equally.
(embodiment 3)
In embodiment 3, the zinc in the plated film (Zn) adhesion amount is 465 μ g/dm 2, in the plated film, Ni:18 weight %; Zn:12 quality %, Cu:70 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.39; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.79, all in condition and range of the present invention.Consequently, in this embodiment 3, the peel strength in the normality BT substrate in the FR substrate is 1.55kN/m, and the peel strength after aging was 1.53kN/m in 2 days, and the deterioration rate is 2%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 0.99kN/m, and the peel strength after the salt acid treatment is 0.93kN/m; The deterioration rate is 6%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.88kN/m; The deterioration rate is 11%, all is good results.
Above result is shown in table 1 equally.
(embodiment 4)
In embodiment 4, the zinc in the plated film (Zn) adhesion amount is 390 μ g/dm 2, in the plated film, Ni:2 weight %; Zn:93 quality %, Cu:5 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.98; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.77, all in condition and range of the present invention.Consequently, in this embodiment 4, the peel strength in the normality BT substrate in the FR substrate is 1.46kN/m, and the peel strength after aging was 1.28kN/m in 2 days, and the deterioration rate is 12%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 1.01kN/m, and the peel strength after the salt acid treatment is 0.86kN/m; The deterioration rate is 15%, and further, the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.92kN/m; The deterioration rate is 9%, all is good results.
Above result is shown in table 1 equally.
(embodiment 5)
In embodiment 5, the zinc in the plated film (Zn) adhesion amount is 378 μ g/dm 2, in the plated film, Ni:40 weight %; Zn:36 quality %, Cu:24 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.47; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.37, all in condition and range of the present invention.The result is, in this embodiment 5, the peel strength in the normality BT substrate in the FR substrate is 1.48kN/m, and the peel strength after aging was 1.43kN/m in 2 days, and the deterioration rate is 3%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 1.04kN/m, and the peel strength after the salt acid treatment is 0.91kN/m; The deterioration rate is 13%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.93kN/m; The deterioration rate is 11%, all is good results.
Above result is shown in table 1 equally.
(embodiment 6)
In embodiment 6, the zinc in the plated film (Zn) adhesion amount is 617 μ g/dm 2, in the plated film, Ni:18 weight %; Zn:12 quality %, Cu:70 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.39; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.79, all in condition and range of the present invention.The result is, in this embodiment 6, the peel strength in the normality BT substrate in the FR substrate is 1.45kN/m, and the peel strength after aging was 1.42kN/m in 2 days, and the deterioration rate is 2%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 1.10kN/m, and the peel strength after the salt acid treatment is 0.87kN/m; The deterioration rate is 21%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.98kN/m; The deterioration rate is 11%, all is good results.
Above result is shown in table 1 equally.
(embodiment 7)
In embodiment 7, the zinc in the plated film (Zn) adhesion amount is 1860 μ g/dm 2, in the plated film, Ni:7 weight %; Zn:9 quality %, Cu:84 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.56; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.92, all in condition and range of the present invention.Consequently, in this embodiment 7, the peel strength in the normality BT substrate in the FR substrate is 1.48kN/m, and the peel strength after aging was 1.40kN/m in 2 days, and the deterioration rate is 5%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 1.02kN/m, and the peel strength after the salt acid treatment is 0.98kN/m; The deterioration rate is 4%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.96kN/m; The deterioration rate is 2%, all is good results.
Above result is shown in table 1 equally.
(embodiment 8)
In embodiment 8, the zinc in the plated film (Zn) adhesion amount is 746 μ g/dm 2, in the plated film, Ni:47 weight %; Zn:30 quality %, Cu:23 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.39; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.33, all in condition and range of the present invention.Consequently, in this embodiment 8, the peel strength in the normality BT substrate in the FR substrate is 1.47kN/m, and the peel strength after aging was 1.46kN/m in 2 days, and the deterioration rate is 1%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 1.03kN/m, and the peel strength after the salt acid treatment is 0.95kN/m; The deterioration rate is 8%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.95kN/m; The deterioration rate is 0%, all is good results.
Above result is shown in table 1 equally.
(embodiment 9)
In embodiment 9, the zinc in the plated film (Zn) adhesion amount is 220 μ g/dm 2, in the plated film, Ni:20 weight %; Zn:69 quality %, Cu:11 quality %, formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.78; Formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.35, all in condition and range of the present invention.Consequently, in this embodiment 9, the peel strength in the normality BT substrate in the FR substrate is 1.45kN/m, and the peel strength after aging was 1.42kN/m in 2 days, and the deterioration rate is 2%.
In addition, the normality peel strength of normality BT substrate (under the harsh environment) is 1.06kN/m, and the peel strength after the salt acid treatment is 0.92kN/m; The deterioration rate is 13%, moreover the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.98kN/m; The deterioration rate is 11%, all is good results.
Above result is shown in table 1 equally.
As stated, in the coating of embodiment, the zinc adhesion weight of per unit area is 220 μ g/dm 2~ 1860 μ g/dm 2, the normality peel strength in the FR-4 substrate is 1.45kN/m ~ 1.56kN/m, and heat-resisting peel strength is 1.20kN/m ~ 1.53kN/m, and the deterioration rate all has good normality peel strength and heat-resisting peel strength in the scope below 18%.
In addition, the normality peel strength in the BT substrate is the scope of 0.99kN/m ~ 1.10kN/m.Peel strength after the processing in hydrochloric acid/sulfuric acid-hydrogen peroxide liquid is respectively 0.85kN/m ~ 0.93kN/m, 0.86kN/m ~ 0.98kN/m, and the deterioration rate is respectively 4% ~ 21%, 0% ~ 14%, has good properties.
(comparative example 1 ~ 7)
Form copper nickel zinc layer with following condition changing bath composition.The ratio that exists of the zinc adhesion amount of per unit area and the nickel in the plated film, zinc, copper is shown in table 2.
(the electroplate liquid component of comparative example 1)
Ni:13g/L, Zn:5g/L, Cu:0g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of comparative example 2)
Ni:13g/L, Zn:0g/L, Cu:6.5g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of comparative example 3)
Ni:0g/L, Zn:5g/L, Cu:0.5g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of comparative example 4)
Ni:13g/L, Zn:15g/L, Cu:0.9g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of comparative example 5)
Ni:15g/L, Zn:0.1g/L, Cu:3g/L, sulfuric acid (H 2SO 4): 8.5g/L
(the electroplate liquid component of comparative example 6)
Ni:3g/L, Zn:16g/L, Cu:0.1g/L, sulfuric acid (H 2SO 4): 1g/L
(the electroplate liquid component of comparative example 7)
Ni:13g/L, Zn:3g/L, Cu:0.5g/L, sulfuric acid (H 2SO 4): 1g/L
(the electroplate liquid component of comparative example 8)
Ni:40g/L, Zn:3g/L, Cu:0.1g/L, sulfuric acid (H 2SO 4): 1g/L
(the electroplate liquid component of comparative example 9)
Ni:32g/L, Zn:0.05g/L, Cu:3.4g/L, sulfuric acid (H 2SO 4): 1g/L
(the electroplate liquid component of comparative example 2)
Ni:25g/L, Zn:16g/L, Cu:0.05g/L, sulfuric acid (H 2SO 4): 1g/L
(current density) 2.5A/dm 2~ 30A/dm 2
(comparative example 1)
In comparative example 1, do not have copper in the plated film, and the ratio that exists of the nickel in the plated film surpasses 50 quality %, exceed the scope of the invention.And formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.49, and formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.00, not in condition and range of the present invention.
In this comparative example 1, the peel strength in the normality BT substrate in the FR substrate is 1.50kN/m, and the peel strength after aging was 1.47kN/m in 2 days, and the deterioration rate is 2%.And the normality peel strength of normality BT substrate (under the harsh environment) is 0.98kN/m, and the peel strength after the salt acid treatment is 0.15kN/m; The deterioration rate obviously drops to 85%, and further, the peel strength in anti-sulfuric acid-hydrogen peroxide is 0.75kN/m; The deterioration rate is 24%, and drug resistance all declines to a great extent.Above result is shown in table 2.
(table 2)
Figure BDA00002048136200221
(comparative example 2)
In comparative example 2, do not have zinc in the plated film, and the ratio that exists of the nickel in the plated film surpasses 50 quality %, exceed the scope of the invention.And formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.45, but formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.00, not in condition and range of the present invention.
In this comparative example 2, the peel strength in the normality BT substrate in the FR substrate is 1.51kN/m, and the peel strength after aging was 1.06kN/m in 2 days, and the deterioration rate is 30%, and the heat-resisting peel strength in the FR-4 substrate declines to a great extent.Above result is shown in table 2 equally.
(comparative example 3)
In comparative example 3, the zinc in the plated film (Zn) adhesion amount is 620 μ g/dm 2, but do not have nickel in the plated film, exceed the scope of the invention.And formula 1 (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 1.00, and formula 2 (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.00.
In this comparative example 3; The normality peel strength of normality BT substrate (under the harsh environment) is 0.96kN/m, and the peel strength after the salt acid treatment is 0.65kN/m, and the deterioration rate obviously drops to 32%; Moreover; Peel strength in anti-sulfuric acid-hydrogen peroxide is 0.69kN/m, and the deterioration rate is 28%, and drug resistance all declines to a great extent.Above result is shown in table 2 equally.
(comparative example 4)
In comparative example 4, the adhesion amount of the zinc of per unit area is 2564 μ g/dm 2, exceed the scope of the invention.In this comparative example 4; The normality peel strength of normality BT substrate (under the harsh environment) is 1.02kN/m, and the peel strength after the salt acid treatment is 0.20kN/m, and the deterioration rate obviously drops to 80%; Moreover; Peel strength in anti-sulfuric acid-hydrogen peroxide is 0.62kN/m, and the deterioration rate is 39%, and drug resistance all declines to a great extent.Above result is shown in table 2 equally.
(comparative example 5)
In comparative example 5, the copper that exists in the plated film is 80 quality % nearly, and zinc is that 4 quality %, nickel are 16 quality %, and (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.2, departs from the scope of the present invention.In this comparative example 5, the normality peel strength in the FR-4 substrate is 1.12kN/m, but the peel strength after the salt acid treatment is 1.12kN/m, and the deterioration rate is 25%, and the heat-resisting peel strength in the FR-4 substrate declines to a great extent.Above result is shown in table 2 equally.
(comparative example 6)
In comparative example 6, the zinc that exists in the plated film is 70 quality % nearly, and copper is few to 6 quality %, and therefore (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.20, departs from the scope of the present invention.In this comparative example 6, the normality peel strength in the BT substrate is 1.04kN/m, but the peel strength after the salt acid treatment is 0.16kN/m, and the deterioration rate is greatly to 85%, and drug resistance (hydrochloric acid) declines to a great extent.Above result is shown in table 2 equally.
(comparative example 7)
In comparative example 7, the adhesion amount of the zinc of per unit area is few to 150 μ g/dm 2, exceed the scope of the invention.In this comparative example 7, the peel strength after aging was 1.01kN/m in the FR-4 substrate 2 days, and the deterioration rate is greatly to 31%, and thermal endurance declines to a great extent.Above result is shown in table 2 equally.
(comparative example 8)
In comparative example 8, the ratio that exists of the nickel in the plated film surpasses 50 quality %, and (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.27, departs from the scope of the present invention.In this comparative example 8, the peel strength after aging was 1.10kN/m in the FR-4 substrate 2 days, and the deterioration rate is greatly to 23%, and the heat-resisting peel strength in the FR-4 substrate declines to a great extent.Above result is shown in table 2 equally.
(comparative example 9)
In comparative example 9, (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is 0.25, departs from the scope of the present invention.In this comparative example 9, the peel strength after aging was 1.19kN/m in the FR-4 substrate 2 days, and the deterioration rate is greatly to 22%, and the heat-resisting peel strength in the FR-4 substrate declines to a great extent.Above result is shown in table 2 equally.
In comparative example 10, (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is 0.28, departs from the scope of the present invention.In this comparative example 10, the normality peel strength in the BT substrate is 1.01kN/m, but the peel strength after the salt acid treatment is 0.71kN/m, and the deterioration rate is greatly to 30%, and drug resistance (hydrochloric acid) declines to a great extent.Above result is shown in table 2 equally.
Can know that as above the condition optimization of the plating bath of the copper nickel zinc layer of manufacturing the application invention is with Ni:0.1g/L ~ 30g/L, Zn:0.1g/L ~ 12g/L, Cu:0.1g/L ~ 2g/L, sulfuric acid (H 2SO 4): 0.1g/L ~ 10g/L is basic plating bath.
Surpass this concentration range, when the concentration of nickel, zinc or copper becomes big, can produce obstacle to waste water treatment, therefore the condition as plating bath is not good.And, when concentration of component is crossed when low, because of the factors such as concentration change that plating causes, the management of the plating bath difficulty that becomes, and also current efficiency descends terrifically, and therefore the condition as plating bath is not good.
The situation of the matsurface that is applicable to electrolytic copper foil more than has been described, also is same in the electrolytic copper foil of glassy surface having been implemented roughened certainly.Moreover, also be same in the rolled copper foil of having implemented roughened.If used the matsurface of electrolytic copper foil and rolled copper foil; Then on the absolute value of normality peel strength, can occur differently, but can reduce peel strength after heat-resisting peel strength and the sulfuric acid/hydrogen peroxide treatment apart from the relative deterioration rate of normality peel strength because of the difference of the shape of roughened, surface roughness.
Tellite of the present invention with Copper Foil in, be the central topic of invention especially with the optimum condition of selecting copper nickel zinc layer.So, can improve the heat-resisting peel strength of Copper Foil tremendously, and effectively prevent the circuit erosion, make anti-sulfuric acid/hydrogen peroxide property permanent, play consistently effectiveness.
Therefore, can at random select the selection of electrolytic copper foil and rolled copper foil or the selection of matsurface according to purpose, this should be understandable.
Industry applications
As stated, tellite of the present invention with Copper Foil for make with heat after the peel strength deterioration and used copper nickel zinc layer not of resin, can improve the heat-resisting peel strength of Copper Foil tremendously.In addition; Thus; Tellite of the present invention can effectively prevent the circuit erosion with Copper Foil; Being endowed can be permanent, play consistently this new characteristic of drug resistance (anti-sulfuric acid-hydrogen peroxide property); Printed circuit fine pattern (fine pattern) in recent years change and the process of high frequencyization in, as tellite with Copper Foil (especially conductor package substrate use Copper Foil), reach stickup Copper Foil and resin substrate and the tellite (especially conductor package substrate) made is used copper clad laminate, be useful.

Claims (7)

1. a tellite is used Copper Foil, has the layer (below be called " copper nickel zinc layer ") that contains nickel, zinc and copper on the surface of Copper Foil, it is characterized in that,
The zinc adhesion weight of the per unit area of above-mentioned copper nickel zinc layer is 200 μ g/dm 2More than and 2000 μ g/dm 2Below, in the above-mentioned copper nickel zinc layer, Ni is 1 ~ 50 weight %, and (zinc adhesion amount (quality %))/{ 100-(copper adhesion amount (quality %)) } is more than 0.3, and (copper adhesion amount (quality %))/{ 100-(zinc adhesion amount (quality %)) } is more than 0.3.
2. tellite according to claim 1 is used Copper Foil, it is characterized in that,
On above-mentioned copper nickel zinc layer, has chromate by rete.
3. tellite according to claim 2 is used Copper Foil, it is characterized in that,
Above-mentioned chromate by rete in, the chromium adhesion weight of per unit area is 30 μ g/dm 2More than and 100 μ g/dm 2Below.
4. use Copper Foil according to claim 2 or 3 described tellites, it is characterized in that,
Also has silane coupling agent layer at above-mentioned chromate on by rete.
5. use Copper Foil according to each described tellite in the claim 1 ~ 4, it is characterized in that,
Copper Foil is an electrolytic copper foil, on the matsurface when above-mentioned copper nickel zinc layer is formed on the electrolysis plating or the glassy surface of electrolytic copper foil.
6. use Copper Foil according to each described tellite in the claim 1 ~ 5, it is characterized in that,
Copper Foil is a rolled copper foil.
7. a tellite is used copper clad laminate, and each described tellite is processed with resin with Copper Foil and tellite in the bonding claim 1 ~ 6.
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